CN102276663A - Preparation method of glucosamine sulfate - Google Patents
Preparation method of glucosamine sulfate Download PDFInfo
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Abstract
The invention provides a preparation method of glucosamine sulfate. According to the hydrolysis in the preparation method, chitosan and a bisulfate-containing acidic ionic liquid undergo a hydrolysis reaction in water for 2-5 hours, wherein the quality and volume ratio of chitosan to the bisulfate-containing acidic ionic liquid is 1:3-5, the water amount is 3-6 times the weight of chitosan, and the reaction temperature is 80-140 DEG C. According to the method, there is no acid fog and tail gas during the production process; and the product contains no chloride ion and is safe with no pollution. With the use of the bisulfate-containing acidic ionic liquid, the reaction time is short, the yield is high, the ionic liquid can be repeatedly used, the whole production technology is simple, the purity and the yield of the product obtained is high, the cost is low, and the preparation method provided by the invention is a green, environmentally friendly and high efficient production technology.
Description
Technical field
The invention belongs to electrochemical analysis detection technique field, be specifically related to a kind of preparation method of glucosamine sulphate.
Background technology
Whole world arthritic has 3.55 hundred million people at present.In the area, Asia, it is present that per six philtrums just have a people to suffer from this world of sacroiliitis No.1 disabling property disease glass in certain stage in all one's life, estimate that the sacroiliitis patient of China's Mainland has more than 100,000,000, and number is also in continuous increase.Violent pain can cause the forfeiture of work capacity, is a great damage to social development and human beings'health.
Glucosamine sulphate obviously releasing arthritis and rheumatisant pain and improvement, prevention, treatment and repair connective tissue damage, bone and sacroiliitis inflammation also there is certain curative effect, also help simultaneously healing acute, chronic inflammatory diseases, therefore heart trouble, pneumonia are also had certain curative effect.
Present amino grape vitriol preparation has two approach, article one, approach is that hydrolyzing chitosan obtains glucosamine hydrochloride under the concentrated hydrochloric acid condition, and people such as gondola then Luigi Rovat use the gegenion exchange process or the organic alkali method obtains glucosamine sulphate; Another approach be people such as Xiao Ling and Zhangjiang woods invention be raw material with the chitosan, with sulfuric acid directly the method for degraded prepare glucosamine sulphate.When the preparation glucosamine hydrochloride, use hydrochloric acid in preceding a kind of production process, the pollution that hydrochloric acid mist causes, damage to the environment and workers'health, remaining hydrochloric acid needs a large amount of washing with alcohol again, increase cost, extend manufacture cycle, after the gegenion exchange, need mixture freeze drying process drying, be difficult to freeze-drying because of containing acetone, so be difficult to large-scale industrialization production; The organic alkali method is wanted earlier glucosamine hydrochloride to be changed into glucosamine alkali, and by regulating the add-on of pH control oleum, the glucosamine sulphate that each batch prepares is formed variant, and stably manufactured has certain difficulty.And directly degrade with sulfuric acid, the a large amount of organic solvents of this method consumption, production cost is higher, residual organic solvent, non-monose compound component are greatly affected product purity, still there is gordian technique to need to break through as healthcare products, pharmaceutical applications, moreover the vitriol oils a large amount of in producing are understood corrosion reacting kettle, and it is also difficult to reclaim.
Summary of the invention
For solving above problem, the object of the present invention is to provide a kind of novel method of preparation glucosamine sulphate of green.Present method is selected green catalyzer, obtains the glucosamine sulphate of high purity and yield under short time conditions.
For achieving the above object, the present invention realizes in the following manner:
A kind of preparation method of glucosamine sulphate comprises hydrolysis, decolouring, concentrates and extraction, and the described acidic ion liquid that is hydrolyzed to chitosan and sulfur acid hydrogen salt is hydrolyzed in water and reacted 2～5 hours; Wherein, temperature of reaction is 80～140 ℃, and the mass volume ratio 1: 3～5 of the acidic ion liquid of chitosan and sulfur acid hydrogen salt, the consumption of water are 3～6 times of chitosan mass.
Described decolouring is for adding the activated carbon decolorizing of chitosan 0.5%～1.5% massfraction.Granularity of activated carbon is preferably crossed 100～150 mesh sieves, and bleaching temperature is controlled at 75～85 ℃, and bleaching time is 1～1.5 hour.
The filtrate heating that described simmer down to decolouring after-filtration obtains concentrates removes moisture, and thickening temperature preferably is controlled at 70～100 ℃.
Described extraction was stirred 1～2 hour for add the organic solvent of 2～4 times of volumes of concentrated solution in the concentrated solution that obtains after concentrating, and left standstill 2～3 hours, and crystallization is separated out, and filtered, and obtained crude product; Wherein, organic solvent is alcohols or ketones solvent, particular methanol, ethanol, dehydrated alcohol, propyl alcohol or acetone.The crude product for preparing is used with respect to 2～4 times soaked in absolute ethyl alcohol of crude product quality 2～3 hours agitation and filtration, drying.
The acidic ion liquid of described sulfur acid hydrogen salt is preferably Methylimidazole class hydrosulfate ionic liquid or pyridines hydrosulfate ionic liquid (accompanying drawing is the ionic liquid general structure).Methylimidazole class hydrosulfate ionic liquid is preferably 1-H-3-Methylimidazole hydrosulfate ionic liquid, 1-propyl group semi-annular jade pendant acidic group-3-Methylimidazole hydrosulfate ionic liquid, 1-butyl-3-Methylimidazole hydrosulfate ionic liquid, and pyridines hydrosulfate ionic liquid is preferably normal-butyl pyridine hydrosulfate ionic liquid.
The chitosan that the present invention uses has no special requirements and commercially availablely all can use, and preferably adopting specification is low viscous chitosan, i.e. viscosity＜200mpa.s.The acidic ion liquid of described sulfur acid hydrogen salt has no special requirements, and all can adopt commercially available or make by oneself to synthesize to obtain.
The preparation method of above-mentioned glucosamine sulphate specifically may further comprise the steps:
A) hydrolysis: the acidic ion liquid of sulfur acid hydrogen salt is warming up to 50～60 ℃, ratio in the mass volume ratio 1: 3～5 of the acidic ion liquid of chitosan and sulfur acid hydrogen salt adds chitosan again, 3～6 times the water that adds chitosan mass simultaneously, the stirring that progressively heats up makes after the chitosan dissolving, be warming up to 80～140 ℃, insulation reaction 2～5 hours;
B) decolouring: after hydrolysis finishes, add the activated carbon decolorizing of chitosan 0.5%～1.5% massfraction again, filter;
C) filtrate concentrates: above-mentioned filtrate is concentrated, remove moisture;
D) extraction: in concentrated solution, add the organic solvent of 2～4 times of volumes, stirred 1～2 hour, left standstill 2～3 hours, crystallization is separated out, filter and obtain crude product;
E) refining: crude product is used with respect to 2～4 times soaked in absolute ethyl alcohol of crude product quality 2～3 hours, and agitation and filtration leaches crystallization, drying.
The Methylimidazole class hydrosulfate ionic liquid molecules formula that the present invention uses is as follows:
The pyridines hydrosulfate ionic liquid molecules formula that the present invention uses is as follows:
Advantage of the present invention compared with the prior art is:
(1) preparation method of the present invention does not have acid mist and tail gas in process of production, can not pollute operator and environment, and be the production technique of environmental protection.
(2) do not introduce chlorion in the preparation process, product is sodium chloride-containing not, and cardiovascular diseases and nephrotic all can take, and is arthritic's the good medicine of curing the disease.
(3) the present invention innovates the acidic ion liquid of use sulfur acid hydrogen salt as solvent and catalyzer, particularly Methylimidazole and pyridines hydrosulfate ionic liquid, add-on is few when hydrolysis, catalytic capability is outstanding, further shorten the reaction times, make chitosan be dissolved into homogeneous phase, shorten the reaction times greatly, it is low to consume energy.And ionic liquid corrodibility is little, prolongs the work-ing life of reactor greatly, saves cost, and whole process of preparation technology is simple.Reacting completely the back ionic liquid can recycling, and rate of recovery height because stability is very good, is reused more than 6 times efficient and do not seen reduction.
(4) product purity of traditional technology preparation is about 99.0%, and the present invention adopts the acidic ion liquid acidic ion liquid of sulfur acid hydrogen salt can obtain purity at the glucosamine sulphate more than 99.5% as reaction solvent and catalyzer hydrolysis, and yield is also high by 10～15% than using mineral acid catalysis.
(5) raw material of the method for traditional preparation process glucosamine sulphate employing is a chitin; and the present invention adopts chitosan (poly-dextrose amine (1-4)-2-amino-B-D glucose) to be as the raw material advantage: chitosan is the deacetylated product of chitin, also is one of elite in the chitin.Find in the research process that chitosan solvability under acidic conditions is better, with the acidic ionic liquid precursor reactant time, consume acidic ion liquid seldom, raw material also is easy to be dissolved into homogeneous phase simultaneously.
Embodiment
Embodiment 1
Take by weighing 10Kg chitosan (Aladdin reagent (Shanghai) Co., Ltd., specification: low viscosity), in the vacuum reaction still, add 50 liters of 1-H-3-Methylimidazole hydrosulfate ionic liquids, be warming up to about 55 ℃, open and stir, open opening for feed, with the chitosan input, and add 50Kg distilled water, the stirring that progressively heats up makes after the chitosan dissolving, 90 ℃ of control reaction temperature, the insulation reaction time is 3.5 hours.After hydrolysis is finished, drop into gac decolouring 1h under 80 ℃ of mistake 100 mesh sieves of 100 grams.Change the feed liquid after the decolouring over to vacuum filtration groove suction filtration, filtrate goes to the vacuum concentration still again, temperature is controlled at 83 ℃, concentrate and remove all moisture, the dehydrated alcohol that adds 3 times of volumes of concentrated solution in concentrated solution is opened to stir fully and was stirred 1.5 hours, and room temperature left standstill 2 hours, crystallization is separated out, and suction filtration obtains crude product.Put crude product into soaking compartment, 3 times of soaked in absolute ethyl alcohol of usefulness crude product quality 2 hours, centrifuge dripping ethanol, going to drying machine is dry under 50 ℃ of conditions in temperature, obtains glucosamine sulphate 6.2Kg.The glucosamine sulphate yield is 62%.
Wherein, 1-H-3-Methylimidazole hydrosulfate ionic liquid ([Hmim] HSO
4) synthetic by the following method obtaining:
Add the 8.2gN-Methylimidazole to the 250ml there-necked flask, in ice bath, be cooled to 0～5 ℃, under vigorous stirring, begin to drip the vitriol oil of 10.2g98% and the diluent of 10ml water, last 30min.Dropwise and remove ice bath, room temperature continues to stir 2h.Reactant removes 75 ℃ of following underpressure distillation and anhydrates, and gets water white little sticking ionic liquid [Hmim] HSO
4
Embodiment 2
Take by weighing the 10Kg chitosan, in the vacuum reaction still, add 35 liters of 1-propyl group semi-annular jade pendant acidic groups-3-Methylimidazole hydrosulfate ionic liquid, be warming up to 60 ℃, open and stir, open opening for feed, the chitosan input, and adding 30Kg distilled water, after the stirring that progressively heats up makes that chitosan dissolves, 80 ℃ of control reaction temperature, the insulation reaction time is 2.5 hours.After hydrolysis is finished, drop into 150 and restrained the gac of 100 mesh sieves at 85 ℃ of 1.5h that decolour down.Change the feed liquid after the decolouring over to vacuum filtration groove suction filtration, filtrate goes to the vacuum concentration still again, and temperature is controlled at 93 ℃, concentrates to remove all moisture.The methyl alcohol that adds 3 times of volumes in concentrated solution is opened to stir fully and was stirred 1.5 hours, and room temperature left standstill 2 hours, and crystallization is separated out, and suction filtration obtains crude product.Put crude product into soaking compartment, 2 times of soaked in absolute ethyl alcohol of usefulness crude product quality 3 hours, centrifuge dripping ethanol, going to drying machine is dry under 50 ℃ of conditions in temperature, obtains glucosamine sulphate 6.7Kg.The glucosamine sulphate yield is 67%.
Wherein, 1-propyl group semi-annular jade pendant acidic group-3-Methylimidazole hydrosulfate ionic liquid ([HSO
3(CH
2)
3Mim] HSO
4) synthetic by the following method obtaining:
1. precursor zwitter-ion 1-propyl group semi-annular jade pendant acidic group-3-Methylimidazole [SO
3(CH
2)
3Mim] synthetic
With 5.0g (40.9mmol) 1,3-propyl group semi-annular jade pendant acid lactone is dissolved in the 40ml acetone, the there-necked flask that adds 250ml, thing to be mixed is cooled in ice bath after 0 ℃, drip the mixture of 3.36g (40.9mmol) N-Methylimidazole and 40ml acetone, last 30min, remove ice bath after dropwising, room temperature reaction spends the night.
Reaction removes by filter acetone after finishing, and the gained white solid is washed 3～4 times with ether again, and 80 ℃ of dried overnight get finished product in vacuum environment at last.
2. with the vitriol oil of precursor zwitter-ion 1-propyl group semi-annular jade pendant acidic group-3-Methylimidazole of preparing and 98% mixed in molar ratio with 1: 1,80 ℃ are stirred 4h and get water white transparency mucus.With the mucus that obtains with toluene and each washed twice of ethyl acetate, 100 ℃ of following vacuum-drying spend the night 1-propyl group semi-annular jade pendant acidic group-3-Methylimidazole hydrosulfate ionic liquid.
Embodiment 3
Take by weighing the 10Kg chitosan, in the vacuum reaction still, add 40 liters of 1-butyl-3-Methylimidazole hydrosulfate ionic liquid, be warming up to about 55 ℃, open and stir, open opening for feed, the chitosan input, and adding 60Kg distilled water, after the stirring that progressively heats up makes that chitosan dissolves, 100 ℃ of control reaction temperature, the insulation reaction time is 2.0 hours.After hydrolysis is finished, drop into 50 and restrained the gac of 150 mesh sieves at 80 ℃ of 1.5h that decolour down.Change the feed liquid after the decolouring over to vacuum filtration groove suction filtration, filtrate goes to the vacuum concentration still again, and temperature is controlled at 80 ℃, concentrates to remove all moisture.The acetone that adds 2 times of volumes in concentrated solution is opened to stir fully and was stirred 1.5 hours, and room temperature left standstill 3 hours, and crystallization is separated out, and suction filtration obtains crude product.Put crude product into soaking compartment,, cleaned 2 hours with 4 times of soaked in absolute ethyl alcohol of crude product quality, centrifuge dripping ethanol, going to drying machine is dry under 50 ℃ of conditions in temperature, obtains glucosamine sulphate 6.4Kg.The glucosamine sulphate yield is 64%.
Wherein, butyl-3-Methylimidazole hydrosulfate ionic liquid ([Bmim] HSO
4) prepare by the following method:
1. bromination 1-butyl-3-Methylimidazole ([Bmim] Br) is synthetic
8.2g (0.1mol) N-Methylimidazole is placed the 150ml there-necked flask, be heated to 65 ℃, begin slowly to drip 16.44g (0.12mol) bromination of n-butane under the violent stirring, last 1h, after dropwising, continue to be warming up to 90 ℃ of reaction 6h and obtain water white transparency mucus.After reaction stops, using ethyl acetate washing reaction liquid 3-4 time, residual ethyl acetate is removed in underpressure distillation, obtains white solid [Bmim] Br.
By [Bmim] Br to [Bmim] HSO
4Building-up process
[Bmim] the Br 21.9g (0.1mol) that prepared beforehand is good is dissolved in 40mlCH
2Cl
2In, in ice bath, stir and be cooled to 0 ℃, slowly add 98% vitriol oil 10g (0.1mol), treat to begin heating, stirring and refluxing 2d after the whole addings of sulfuric acid.The pungency gas evolution is constantly arranged in the reaction process, and reaction solution becomes orange-yellow gradually.Stop heating behind the 2d, solvent C H is removed in underpressure distillation
2Cl
2And a spot of water that brings in the sulphuric acid soln, obtain the little sticking ionic liquid of lark [Bmim] HSO
4
Embodiment 4
Take by weighing the 10Kg chitosan, in the vacuum reaction still, add 40 liters of normal-butyl pyridine hydrosulfate ionic liquids, be warming up to 50 ℃, open and stir, open opening for feed, the chitosan input, and adding 40Kg distilled water, after the stirring that progressively heats up makes that chitosan dissolves, 140 ℃ of control reaction temperature, the insulation reaction time is 5.0 hours.After hydrolysis is finished, drop into 100 and restrained the gac of 100 mesh sieves at 80 ℃ of 1h that decolour down.Change the feed liquid after the decolouring over to vacuum filtration groove suction filtration, filtrate goes to the vacuum concentration still again, temperature is controlled at 100 ℃, concentrate and remove all moisture, the propyl alcohol that adds 4 times of volumes of concentrated solution in concentrated solution is opened to stir fully and was stirred 1.5 hours, and room temperature left standstill 2 hours, crystallization is separated out, and suction filtration obtains crude product.Put crude product into soaking compartment, 3 times of soaked in absolute ethyl alcohol of usefulness crude product quality 2 hours, centrifuge dripping ethanol, going to drying machine is dry under 50 ℃ of conditions in temperature, obtains glucosamine sulphate 6.0Kg.The glucosamine sulphate yield is 60%.
Wherein, normal-butyl pyridine hydrosulfate ionic liquid [BPy] HSO
4Prepare by the following method:
8mL (0.1mol) pyridine and the positive n-butyl bromide of 10.8mL (0.1mol) are added in the 100mL round-bottomed flask, react 12h at 90 ℃ under the mechanical stirring, add 13.8g (0.1mol) sulfuric acid monohydrate hydrogen sodium again, continue at 90 ℃ and continue to stir 1h, be cooled to room temperature, suction filtration, filtrate vacuum-drying gets the garnet transparent liquid.
The glucosamine sulphate that method according to embodiment 1～4 is prepared carries out the performance quality detection, the results are shown in Table 1:
Table 1
Comparative Examples
According to the method for embodiment 2, only the acidic ion liquid of sulfur acid hydrogen salt is replaced with 35 liters of volumetric concentrations and be 70% sulfuric acid and react, the experimental result contrast sees Table 2:
Table 2
As shown in Table 2, and use mineral acid relatively, the acidic ion liquid of sulfur acid hydrogen salt as catalyzer, is obtained higher product yield in the short time, less and reusable performance is strong to the corrodibility of reactor, be the ideal hydrolyst.
Claims (10)
1. the preparation method of a glucosamine sulphate comprises hydrolysis, decolouring, concentrates and extraction, it is characterized in that described acidic ion liquid with chitosan and the sulfur acid hydrogen salt hydrolysis reaction 2～5 hours in water that is hydrolyzed to; Wherein, temperature of reaction is 80～140 ℃, and the mass volume ratio 1: 3～5 of the acidic ion liquid of chitosan and sulfur acid hydrogen salt, the consumption of water are 3～6 times of chitosan mass.
2. the preparation method of glucosamine sulphate according to claim 1 is characterized in that described decolouring is for adding the activated carbon decolorizing of chitosan 0.5%～1.5% massfraction.
3. the preparation method of glucosamine sulphate according to claim 1 is characterized in that the filtrate heating that described simmer down to decolouring after-filtration obtains concentrates removal moisture.
4. the preparation method of glucosamine sulphate according to claim 1 is characterized in that the organic solvent of described extraction for 2～4 times of volumes of adding concentrated solution in the concentrated solution that obtains after concentrating, and stirs 1～2 hour, left standstill 2～3 hours, crystallization is separated out, and filters, and obtains crude product; Wherein, organic solvent is alcohols or ketones solvent.
5. the preparation method of glucosamine sulphate according to claim 4 is characterized in that the crude product for preparing being used with respect to 2～4 times soaked in absolute ethyl alcohol of crude product quality 2～3 hours agitation and filtration, drying.
6. the preparation method of glucosamine sulphate according to claim 1, the acidic ion liquid that it is characterized in that described sulfur acid hydrogen salt is Methylimidazole class hydrosulfate ionic liquid or pyridines hydrosulfate ionic liquid.
7. the preparation method of glucosamine sulphate according to claim 6, it is characterized in that described Methylimidazole class hydrosulfate ionic liquid is 1-H-3-Methylimidazole hydrosulfate ionic liquid, 1-propyl group semi-annular jade pendant acidic group-3-Methylimidazole hydrosulfate ionic liquid, 1-butyl-3-Methylimidazole hydrosulfate ionic liquid, pyridines hydrosulfate ionic liquid is a normal-butyl pyridine hydrosulfate ionic liquid.
8. the preparation method of glucosamine sulphate according to claim 2 is characterized in that described granularity of activated carbon was 100～150 mesh sieves, and bleaching temperature is controlled at 75～85 ℃, and bleaching time is 1～1.5 hour.
9. the preparation method of glucosamine sulphate according to claim 1 is characterized in that described thickening temperature is controlled at 70～100 ℃.
10. the preparation method of glucosamine sulphate according to claim 1 is characterized in that described method specifically may further comprise the steps:
A) hydrolysis: the acidic ion liquid of sulfur acid hydrogen salt is warming up to 50～60 ℃, ratio in the mass volume ratio 1: 3～5 of the acidic ion liquid of chitosan and sulfur acid hydrogen salt adds chitosan again, 3～6 times the water that adds chitosan mass simultaneously, the stirring that progressively heats up makes after the chitosan dissolving, be warming up to 80～140 ℃, insulation hydrolysis reaction 2～5 hours;
B) decolouring: after hydrolysis finishes, add the activated carbon decolorizing of chitosan 0.5%～1.5% massfraction again, filter;
C) filtrate concentrates: above-mentioned filtrate is concentrated, remove moisture;
D) extraction: add the organic solvent of 2～4 times of volumes of concentrated solution in concentrated solution, stirred 1～2 hour, left standstill 2～3 hours, crystallization is separated out, and filters and obtains crude product;
E) refining: crude product is used with respect to 2～4 times soaked in absolute ethyl alcohol of crude product quality 2～3 hours, and agitation and filtration leaches crystallization, drying.
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| CN103182285A (en) * | 2011-12-30 | 2013-07-03 | 北京有色金属研究总院 | Product and method for inhibiting acid mist diffusion during electrodeposition process |
| CN105440088A (en) * | 2015-11-20 | 2016-03-30 | 南方科技大学 | Glucosamine mixed strontium salt as well as preparation method and application thereof |
| CN106117276A (en) * | 2016-06-27 | 2016-11-16 | 梅庆波 | A kind of preparation method of glucosamine sulfate |
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| CN110776538A (en) * | 2019-12-02 | 2020-02-11 | 山东润德生物科技有限公司 | Preparation method of low-potassium or low-sodium glucosamine sulfate |
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| CN102807630A (en) * | 2012-06-26 | 2012-12-05 | 东营天东制药有限公司 | Low-molecular-weight chitosan and glucosamine co-production technology |
| CN102807630B (en) * | 2012-06-26 | 2014-12-10 | 东营天东制药有限公司 | Low-molecular-weight chitosan and glucosamine co-production technology |
| CN105440088A (en) * | 2015-11-20 | 2016-03-30 | 南方科技大学 | Glucosamine mixed strontium salt as well as preparation method and application thereof |
| CN106117276A (en) * | 2016-06-27 | 2016-11-16 | 梅庆波 | A kind of preparation method of glucosamine sulfate |
| CN106117276B (en) * | 2016-06-27 | 2018-11-30 | 山东润德生物科技有限公司 | A kind of preparation method of Glucosamine Sulphate |
| CN110590869A (en) * | 2019-10-09 | 2019-12-20 | 山东润德生物科技有限公司 | Preparation method of N-acetylglucosamine |
| CN110684059A (en) * | 2019-10-23 | 2020-01-14 | 山东润德生物科技有限公司 | Preparation method of D-glucosamine sulfate |
| CN110684059B (en) * | 2019-10-23 | 2020-08-28 | 山东润德生物科技有限公司 | Preparation method of D-glucosamine sulfate |
| CN110713501A (en) * | 2019-11-08 | 2020-01-21 | 山东润德生物科技有限公司 | Preparation method of glucosamine calcium sulfate salt |
| CN110680906A (en) * | 2019-11-12 | 2020-01-14 | 山东润德生物科技有限公司 | Glucosamine bone glue peptide calcium granules |
| CN110680906B (en) * | 2019-11-12 | 2020-10-09 | 山东润德生物科技有限公司 | Glucosamine bone glue peptide calcium granules |
| CN110776538A (en) * | 2019-12-02 | 2020-02-11 | 山东润德生物科技有限公司 | Preparation method of low-potassium or low-sodium glucosamine sulfate |
| CN110776538B (en) * | 2019-12-02 | 2021-02-12 | 山东润德生物科技有限公司 | Preparation method of low-potassium or low-sodium glucosamine sulfate |
| CN111777651A (en) * | 2020-07-20 | 2020-10-16 | 山东润德生物科技有限公司 | Preparation method of D-glucosamine sulfate and stirring equipment |
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